Elastomer and vulcanizate compositions having desirable high temperature properties

ABSTRACT

Compositions including a thermoplastic elastomer or thermoplastic vulcanizate derived from a styrenic block copolymer having a reactive or crosslinkable hard block including aromatic vinyl repeat units and also preferably a crosslinkable soft block, and a non-olefin thermoplastic polymer or copolymer and preferably a compatibilizer such as the reaction product of a non-olefin thermoplastic polymer and a functionalized polymer such as a maleic anhydride functionalized styrenic block copolymer that is compatible with the styrenic block copolymer having a reactive or crosslinkable hard block, and optionally a linking compound. The vulcanizates are prepared by crosslinking the styrenic block copolymer in the presence of the non-olefin thermoplastic polymer and a suitable crosslinking agent, and optionally the compatibilizer, preferably utilizing dynamic vulcanization. In a further embodiment, thermoplastic vulcanizate compositions are provided including the styrenic block copolymer, a polyolefin polymer or copolymer, a non-olefin thermoplastic polymer and the compatibilizer.

CROSS REFERENCE

This application is a divisional application of pending U.S. patentapplication Ser. No. 11/709,977, filed Feb. 23, 2007 for ELASTOMER ANDVULCANIZATE COMPOSITIONS HAVING DESIRABLE HIGH TEMPERATURE PROPERTIES,herein fully incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to compositions including a thermoplasticelastomer or thermoplastic vulcanizate derived from a styrenic blockcopolymer having a reactive or crosslinkable hard block includingaromatic vinyl repeat units and also preferably a crosslinkable softblock, and a non-olefin thermoplastic polymer or copolymer andpreferably a compatibilizer such as the reaction product of a non-olefinthermoplastic polymer and a functionalized polymer such as a maleicanhydride functionalized styrenic block copolymer that is compatiblewith the styrenic block copolymer having a reactive or crosslinkablehard block, and optionally a linking compound. The vulcanizates areprepared by crosslinking the styrenic block copolymer in the presence ofthe non-olefin thermoplastic polymer and a suitable crosslinking agent,and optionally the compatibilizer, preferably utilizing dynamicvulcanization. In a further embodiment, thermoplastic vulcanizatecompositions are provided including the styrenic block copolymer, apolyolefin polymer or copolymer, a non-olefin thermoplastic polymer orcopolymer with a melting point higher than the polyolefin, and thecompatibilizer. When a crosslinkable hard block and a crosslinkable softblock are present in the styrenic block copolymer, a tightercrosslinking network can be formed during crosslinking, therebyimproving the properties of the composition. The compositions exhibitdesirable high temperature properties and are suitable in a wide varietyof applications.

BACKGROUND OF THE INVENTION

Manufacturers of molded or formed parts, such as automobile parts, wirecoatings, durable and disposable goods parts, medical parts, soft touchovermolded parts, extruded parts or co-extruded parts, building andconstruction parts, appliance parts, electrical parts, industrial toolparts, food and potable water contact parts, housewares, sporting goods,consumer and industrial applications, or the like often choose aparticular resin such as a thermoplastic elastomer or vulcanizate basedon factors such as processability, chemical resistance, and/ormechanical properties, or the like. The inventors believed there was aneed in the art to provide a composition that offers desirableproperties such as chemical resistance and low swelling in fluids athigh temperature.

Many different types of thermoplastic elastomer blends and vulcanizatesare known in the art wherein the rubber component includes astyrene-containing rubber, a natural rubber, synthetic rubber, EPDMrubber, and a crystalline component can be, for example, olefins such aspolyethylene or polypropylene, polyesters and even polyamides, orcombinations thereof. Examples of such compositions are as follows.

U.S. Pat. No. 5,089,557 relates to polymeric blends of astyrene/acrylonitrile grafted elastomer, nylon, a compatibilizer resinparticularly styrene/acrylonitrile/maleic anhydride copolymer, and acore/shell grafted elastomer having an acid functionalized shellreportedly having improved notch sensitivity.

U.S. Pat. No. 5,177,149 relates to thermoplastic blends of amorphouspolyamide resins with poly(alkenyl aromatic) resins reportedly havingimproved properties over previously known blends.

U.S. Pat. No. 5,248,726 relates to polymer blend compositions whichcomprise 99-1 weight percent polyamide resin, 1-99 weight percent ABSresin, and 1-100 phr of carboxylated nitrile rubbers, based upon thetotal weight of the polyamide and ABS resin.

U.S. Pat. No. 6,548,181 relates to a flexible polyamide compositioncontaining at least 50 parts by weight of non-crosslinked rubber per 50parts by weight of polyamide and the production thereof. The polyamidehas a molecular weight such that the melt viscosity at the processingtemperature is at most 300 Pa·s, preferably at most 200 Pa·s. Therubber's Mooney viscosity is at least 40, most preferable is a rubberwith a Mooney viscosity of at least 60. The rubber has beenfunctionalized. Preferably, a combination of a functionalized and anon-functionalized rubber is used. The rubber particles in the polyamidematrix have a particle size of at most 5 μm, preferably at most 3 μm.

U.S. Pat. No. 6,747,094 relates to a high-impact thermoplastic resincomposition comprising: (A) 5 to 95 parts by weight of a thermoplasticelastomer comprising a partially or completely crosslinked saturatedrubber-like polymer and a polyolefinic resin and/or a polystyrene-basedresin, or a mixture of said thermoplastic elastomer and a polyolefinicresin; and (B) 95 to 5 parts by weight of at least one thermoplasticresin selected from the group consisting of polystyrene-based resins,polyamide-based resins, polyurethane-based resins, polycarbonate-basedresins, acrylic resins, polyacetal-based resins and polyphenylenesulfide-based resins, the total of the components (A) and (B) being 100parts by weight, wherein the amount of the saturated rubber-like polymerin the composition is 1 to 40% by weight.

U.S. Pat. No. 6,908,573 relates to a screw for a multiple screw extrudercomprising at least two conveying sections for transporting acomposition comprising a polymeric resin from the feed end to thedischarge end of the extruder; and at least two mixing sectionscomprising screw elements having two flights, wherein the ratio of thelength to diameter ratio of the sum of the mixing sections to the lengthto diameter ratio of the screw is about 0.17 to about 0.5 and whereinthe conveying sections are separated by at least one mixing section.

U.S. Pat. No. 7,041,741 relates to toughened thermoplastic compositionscomprising a thermoplastic polymer toughened by the inclusion of athermoplastic elastomer derived from a particulate rubber dynamicallyvulcanized in the presence of a matrix polymer. The toughenedthermoplastic composition exhibits properties including toughness,improved impact resistance, and improved hardness. The compositions areutilized wherever toughened, high performance polymers are desired. Amethod for forming the toughened polymer compositions is also described.Processing methods, such as rotational molding, utilizing the toughenedpolymer compositions are described.

U.S. Pat. No. 7,074,855 relates to a thermoplastic elastomer compositioncomprising (I) 100 parts by weight of at least one block copolymerformed by addition polymerization which is selected among blockcopolymers which comprise a polymer block (A) consisting of aromaticvinyl units and a polymer block (B) consisting of conjugated dienecompound units and which have been crosslinked in the polymer block (A)preferably with a structural unit derived from a (C₁-C₈ alkyl)styreneand/or functional group and among products of hydrogenation of thecopolymers, (II) 10 to 300 parts by weight of a polyolefin, and (III) 0to 300 parts by weight of a softener for rubbers; and a process forproducing the composition. The composition reportedly has excellentstrain recovery at high temperatures. It is also reportedly effectivelyusable in various applications.

U.S. Published Application No. 2006/0178485 relates to a hydrogenateddiene-based copolymer satisfying predetermined conditions, which isobtained by hydrogenating a block copolymer containing at least twopolymer blocks (A) composed mainly of a vinyl aromatic compound and atleast one vinyl aromatic compound-conjugated diene compound copolymerblock (B). The hydrogenated diene-based copolymer is reportedly superiorin processability, flexibility, weather resistance, vibration-dampingproperty and mechanical properties, and reportedly can provide a shapedarticle highly flexible and superior in various properties such asmechanical properties, appearance, mar resistance, weather resistance,heat resistance, vibration-damping property, processability and thelike.

European Patent Application 0 302 510 relates to a polymer blendcomposition comprising from about 20 to 60 weight percent polyamide,from about 30 to 80 weight percent of styrenic component, and from about1 to 25 weight percent of a carboxylated polyolefin elastomer. Inpreferred embodiments, the styrenic component includes carboxylicacid-derived functional groups and the carboxylated polyolefin elastomercomprises a copolymer of ethylene and another olefin compound.

Taiwan Patent No. TW 404965B discloses an impact-resistantpolystyrene/polyamide composition, comprising (a) 50-100 parts by weightof a syndiotactic styrene-based polymer; (b) 1-50 parts by weight of apolyamide; and (c) 0.01-20 parts by weight of a styrene-maleic anhydridecompatibilizer. The invention is characterized by a compatibilizer whichreportedly imparts toughness and flexural strength to the polymer blendof the composition.

SUMMARY OF THE INVENTION

In view of the above considerations, the inventors of the presentapplication have discovered thermoplastic elastomer blend andvulcanizate compositions that exhibit desirable properties, such aschemical resistance and low swelling in fluids at relatively hightemperatures. The compositions include a non-olefin thermoplasticpolymer or copolymer such as Nylon-6 or Nylon-6,6, or the like, and astyrenic block copolymer having a reactive or crosslinkable moiety/sitein at least one hard block and at least one soft block comprising one ormore repeat units, which are the same or different repeat units when twoor more repeat units are present, that are derived from one or moremonomeric units, for example, an olefin monomer, such as ethylene,propylene, or butylene, or a diene monomer such as butadiene, isopreneor combinations thereof, with at least one soft block preferably beingcrosslinkable. In a preferred embodiment, the composition furtherincludes a compatibilizer.

In one embodiment, the composition is a thermoplastic elastomer blend,formed by blending a non-olefin thermoplastic such as polyamide and thestyrenic block copolymer having the reactive hard block above themelting point of the non-olefin thermoplastic. Optionally, butpreferably, one or more compatibilizers such as a reaction product ofpolyamide and maleated styrenic block copolymer are incorporated inand/or formed during the formation of the blend.

In a further embodiment, the reactive sites on the hard block of thestyrenic block copolymer and reactive sites on the soft block whenpresent are reacted in the presence of a molten or melted non-olefinthermoplastic such as polyamide and optionally a compatibilizerutilizing a crosslinking agent to form a thermoplastic vulcanizate.Additional embodiments of the invention include thermoplasticvulcanizates formed from a composition including a styrenic blockcopolymer having a reactive or crosslinkable moiety/site in at least onehard block, and preferably at least one soft block, preferably beingcrosslinkable; a polyolefin polymer or copolymer; a non-olefinthermoplastic polymer or copolymer having a higher melting point thanthe polyolefin, and a compatibilizer, such as formed from the reactionproduct of a non-olefin thermoplastic, a functional group containingstyrenic block copolymer and optionally a linking compound when thenon-olefin thermoplastic and functional group containing styrenic blockcopolymer contain the same functional group or are otherwisenon-reactive with each other, wherein the linking compound forms abridge between the non-olefin thermoplastic and the functional groupcontaining styrenic block copolymer. Vulcanizates are preferablyprepared by subjecting the molten blend mixture to vulcanization underdynamic mixing conditions. Both the thermoplastic elastomer blend andthermoplastic vulcanizate compositions are thermoplastic in nature andthus can be molded and remolded or recycled.

In one aspect of the invention, a thermoplastic composition, comprisinga styrenic block copolymer comprising at least one hard polymer block(A) and at least one soft polymer block (B), wherein at least one unitof the at least one hard polymer block (A) is crosslinkable andindependently includes at least one of (i) an alkyl styrene-derivedfunctional unit and (ii) an aromatic vinyl compound unit having afunctional group, wherein the soft polymer block (B) includes at leastone repeat unit derived from an olefin or a diene; and a non-olefinthermoplastic polymer or copolymer in an amount from about 10 to about1,500 parts per 100 parts by weight of the styrenic block copolymer, andwherein the composition is substantially free of a polyolefin, whereinthe non-olefin thermoplastic includes one or more of polyamide,polyester, poly(phenylene oxide), poly(phenylene sulfide), poly(imide)and poly(sulfone). Optionally, but preferably, one or morecompatibilizers such as a reaction product of a non-olefin thermoplasticsuch as polyamide and maleated styrenic block copolymer are incorporatedin the blend or formed in situ during preparation of the blend.

In another aspect of the invention, a thermoplastic vulcanizatecomposition, comprising a styrenic block copolymer comprising at leastone hard polymer block (A) and at least one soft polymer block (B),wherein one or more units of the at least one hard polymer block (A) arecrosslinkable and independently include at least one of (i) an alkylstyrene-derived functional unit, and (ii) an aromatic vinyl compoundunit having a functional group, wherein the soft polymer block (B)includes at least one repeat unit derived from an olefin or a diene; apolyolefin polymer or copolymer; a non-olefin thermoplastic polymer orcopolymer polyamide in an amount from about 10 to about 1,500 parts per100 parts by weight of the styrenic block copolymer, wherein thenon-olefin thermoplastic polymer or copolymer is one or more ofpolyamide, polyester, poly(phenylene oxide), poly(phenylene sulfide),poly(imide) and poly (sulfone); a compatibilizer; and a crosslinkingagent, wherein the crosslinking agent crosslinks one or more segments ofthe styrenic block copolymer. Preferably, the compatibilizer includes astyrenic block copolymer including one or more crosslinkable functionalgroups independently derived from a compound including a carboxylic acidgroup and/or an anhydride group.

Functional groups in the soft block (B) either introduced duringpolymerization or later on by reactive extrusion can be used for acrosslinking reaction. Vulcanizates are preferably prepared bysubjecting the composition mixture to dynamic vulcanization in thepresence of one or more of appropriate curing agents under melted,mixing conditions. Optionally, but preferably, one or morecompatibilizers, such as a reaction product of polyamide and maleatedstyrenic block copolymer, are incorporated in the blend initially orformed during processing or formation of the vulcanizate. Thevulcanizate composition can be additionally later melt blended with oneor more polymers, such as polyamide, polyester and the like, above theirmelting temperature.

The compatibilizer can have a number of different structures. Thecompatibilizer is an oligomer, a block copolymer, a graft copolymer, ora reaction product of two or more oligomers or polymers which comprisesat least one portion or segment compatible with the styrenic blockcopolymer having a reactive hard block and at least one portion orsegment compatible with a non-olefin thermoplastic polymer such aspolyamide, polyester, PPO and the like. In one embodiment, thecompatibilizer is the reaction product of a functionalized styrenicblock copolymer and a non-olefin functionalized thermoplastic polymer orcopolymer. In a further embodiment, the compatibilizer is the reactionproduct of functionalized styrenic block copolymer, a non-olefinthermoplastic polymer and a linking compound, wherein the functionalgroups of the styrenic block copolymer and the thermoplastic polymer arethe same or are otherwise non-reactive with each other, with the linkingcompound having two or more functional groups, at least one capable ofreacting with functionalized styrenic block copolymer and at least onecapable of reacting with the non-olefin functionalized thermoplasticpolymer. In one embodiment, the compatibilizer is the reaction productof polyamide and functionalized styrenic block copolymer. The functionalgroup in the styrenic block copolymer is optionally, but preferably,maleic anhydride or a carboxylic acid moiety.

The compatibilizer is formed preferably utilizing a melt reactionprocess. The compatibilizer can be formed via an in situ melt mixingand/or dynamic vulcanization process or through multiple step processes.In multiple step processes, a portion of the compatibilizer can beformed in a first reaction process wherein a linking compound is reactedwith either the non-olefin thermoplastic or the functionalized styrenicblock copolymer. In the second process the formed reaction product isreacted with the component, non-olefin thermoplastic or functionalizedstyrenic block copolymer not present in the first reaction product. Theformed reaction product compatibilizer can then be melt blended in adesired further composition. In one embodiment, the compatibilizer ispreferably formed in situ during dynamic vulcanization through reactionof functional groups present on the styrenic block copolymer and anon-olefin thermoplastic such as a polyamide. Accordingly, thecompatibilizer has affinity for both styrenic block copolymer andthermoplastic, such as polyamide, and it, therefore, in a polymercomposition improves compatibility between a styrenic block copolymerhaving at least a reactive hard block and a non-olefin thermoplastic,such as a polyamide.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, the compositions of the present invention arethermoplastic elastomers which are unvulcanized blends of a styrenicblock copolymer, wherein styrenic block copolymer contains a reativemoiety, and a thermoplastic such as polyamide, and optionally,additional components. In a further embodiment, the compositions of thepresent invention are thermoplastic vulcanizates that are vulcanized,preferably dynamically, under melting conditions during which thecomposition is mixed and crosslinked due to the inclusion of acrosslinking agent.

Styrenic Block Copolymer with Reactive Hard Block

The compositions of the present invention include a styrenic blockcopolymer having a reactive or crosslinkable hard block (A) includingaromatic vinyl repeat units. The styrenic block copolymer comprises ahard polymer block (A) having at least one of (i) analkylstyrene-derived functional group or structural unit having at leastone alkyl group containing 1 to 8 carbon atoms combined with the benzenering, and/or (ii) an aromatic vinyl monomer unit having a functionalgroup; and at least one soft polymer block (B) comprising two or morerepeat units, that are the same or different, derived from one or moreof the following monomers, including an olefin monomer, preferablyhaving from 2 to about 12 carbon atoms, such as ethylene, propylene, orbutylene, or a diene, such as butadiene or isoprene, or a combinationthereof, preferably wherein at least one of the soft blocks is alsoreactive or crosslinkable. The styrenic block copolymer can be ahydrogenated product.

The styrenic block copolymer in one preferred embodiment may becrosslinked in the soft polymer block (B) as well as the hard polymerblock (A). In another embodiment, however, the styrenic block copolymeris crosslinkable or crosslinked, not in the soft polymer block (B), butonly in the hard polymer block (A). When the soft and hard segments orblocks both participate in crosslinking, a tighter crosslinking networkis formed.

The crosslinkable hard segment polymer block (A) can be obtained byintroducing at least one of (i) an alkylstyrene-derived structural unitsuch as a (C₁-C₈ alkyl)styrene-derived structural unit and (ii) afunctional group into polymer block (A). Thus, crosslinked structure inthe crosslinkable hard polymer block (A) can be formed through the (i)alkylstyrene-derived structural unit and/or (ii) the functional group.In a further embodiment, an additional functional group can be presentin the soft polymer block (B), in which case, upon crosslinking orcuring, both polymer block (A) and polymer block (B) will containcrosslinks.

The hard polymer block (A) crosslinking sites can contain the (i)alkylstyrene-derived structural unit and/or (ii) the functional group atone end, both ends, or randomly distributed in a molecular chain. Thus,the hard polymer block (A) may be crosslinked at one or more ends,crosslinked at one or more points in its molecular chain, or crosslinkedboth at its one or more ends and at one or more midpoints in itsmolecular chain.

When the styrenic block copolymer is a diblock copolymer (A-B) havingone hard polymer block (A), a triblock copolymer (B-A-B) having one hardpolymer block (A), or a hydrogenated product thereof, at least one ofthe (i) alkylstyrene-derived structural unit and/or (ii) the functionalgroup is present in the hard polymer block (A) and adapted to form acrosslink therein.

When the styrenic block copolymer is a triblock, tetrablock, or highermultiblock copolymer having two or more hard polymer blocks or segments(A) or a hydrogenated product thereof, at least one of the (i)alkylstyrene-derived structural unit and (ii) the functional group maybe present in only one of the two or more hard polymer blocks (A) andadapted to form a crosslinked structure therein, or alternatively, maybe present in two or more of, or all of the hard polymer blocks (A) andthus adapted to form crosslinked structures in all hard polymer blocks(A) present.

Out of the multitude of possibilities for the structure of the styrenicblock copolymer, the copolymer is preferably a hydrogenated product of atriblock copolymer represented by (A-B-A) wherein both (A) hard polymerblocks are crosslinkable or are crosslinked; and/or a hydrogenatedproduct of a pentablock copolymer represented by (A-A-B-A-A) which iscrosslinkable or crosslinked in at least the block (A) end blocks.

Examples of alkylstyrene, including the (C₁-C₈ alkyl)styrene-derivedstructural unit in the hard polymer block (A) include, but are notlimited to, o-alkylstyrene, m-alkylstyrene, p-alkylstyrene,2,4-dialkylstyrene, 3,5-dialkylstyrene, and 2,4,6-trialkylstyrene, eachcontaining 1 to about 8 carbon atoms in the alkyl group, as well ashalogenated alkylstyrenes corresponding to the aforementionedalkylstyrenes except with halogen atoms replacing one or more hydrogenatoms in the alkyl group. Specific examples of such alkylstyrenederivatives constituting the (C₁-C₈ alkyl)styrene-derived structuralunit include o-methylstyrene, m-methylstyrene, p-methylstyrene,2,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene,o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 2,4-diethylstyrene,3,5-diethylstyrene, 2,4,6-triethylstyrene, o-propylstyrene,m-propylstyrene, p-propylstyrene, 2,4-dipropylstyrene,3,5-dipropyl-styrene, 2,4,6-tripropylstyrene, 2-methyl-4-ethylstyrene,3-methyl-5-ethyl-styrene, o-chloromethylstyrene, m-chloromethylstyrene,p-chloromethylstyrene, 2,4-bis(chloro-methyl)-styrene,3,5-bis(chloromethyl)styrene, 2,4,6-tri(chloromethyl)styrene,o-dichloro-methylstyrene, m-dichloromethylstyrene, andp-dichloromethylstyrene.

The hard polymer block (A) may have one or more same or different repeatunits of the alkyl-styrenes or halogenated alkylstyrenes, orcombinations thereof, as the (i) alkylstyrene-derived structural unit.Among the alkylstrene-derived structural units, p-methylstyrene hasexcellent reactivity with crosslinking agents such as bismaleimidecompounds and organic peroxides, and can reliably introduce acrosslinked structure into the hard polymer block (A) and is thus apreferred alkylstyrene-derived structural unit.

In an embodiment where the styrenic block copolymer or its hydrogenatedproduct does not have the (ii) functional group, but instead (i) atleast one alkylstyrene-derived structural unit in the hard polymer block(A) and is crosslinked utilizing the alkylstyrene-derived structuralunit, the content of the (i) alkylstyrene-derived structural unit in thehard polymer block (A) is preferably 1% by weight or more, preferably 5%by weight or more, and further preferably 10% by weight or more based onthe total weight of the hard polymer block (A) of the styrenic blockcopolymer. When the styrenic block copolymer includes two or more hardpolymer blocks (A), the term “weight of the hard polymer block (A)”means the total weight of the two or more hard polymer blocks (A).

Examples of the (ii) functional group, i.e., before crosslinking, in thehard polymer block (A) of the block copolymer include a functional grouphaving one or more active hydrogen atoms, such as functional groupsrepresented by the following formulae: —OH, —SH, —NH₂, —NHR, —CONH₂,—CONHR, —CONH—, —SO₃H, SO₂H, and —SOH, wherein R is a hydrocarbon group;a functional group having a nitrogen atom, such as functional groupsrepresented by the following formulae: —NR₂, >C═NH, >C═N, —CN, —NCO,—OCN, —SCN, —NO, —NO₂, —NCS, —CONR₂, and —CONR—, wherein R₂ is ahydrocarbon group; a functional group having a carbonyl group orthiocarbonyl group, such as a functional group represented by thefollowing formulae: >C═O, C═S, —CH═O, —CH═S, —COOR, and —CSOR₃, whereinR₃ is a hydrocarbon group; an epoxy group, and a thioepoxy group. Theblock copolymer can have one or more of these functional groups in thehard polymer block (A) and can be crosslinked therethrough these (ii)functional groups in the hard polymer block (A).

In an embodiment wherein the styrenic block copolymer is an additionblock copolymer, or its hydrogenated product, which includes at leastone (ii) functional group, but does not include any (i)alkylstyrene-derived structural unit in the hard polymer block (A), andfurther is not crosslinked in the soft polymer block (B), the number of(ii) functional groups is generally from about 1.2 to about 1,000 andpreferably from about 1.6 to about 200 per molecule of the styrenicblock copolymer. In an embodiment where the styrenic block copolymerdoes not have an alkylstyrene-derived structural unit, has a functionalgroup in the hard polymer block (A), and has a further functional groupin the soft polymer block (B), and can be crosslinked in both the hardpolymer block (A) and soft polymer block (B), the number of functionalgroups is generally from about 2.2 to 1,100, and preferably from about1.6 to 230 per molecule of the styrenic block copolymer. In this case,the number of functional groups in the soft polymer block (B) isgenerally from 0.5 to 30 per molecule of the styrenic block copolymer.

In an additional embodiment, when the styrenic block copolymer includesboth the (i) alkylstyrene-derived structural unit and the (ii)functional group in the same or different hard polymer blocks (A), it ispreferred that the content of the alkylstyrene-derived structural unitis from 1 to 90% by weight based on the weight of the hard polymerblocks (A) and the content of the functional group is from 1 to 1,000groups per molecule of the styrenic block copolymer.

In the case of the thermoplastic vulcanizates of the present invention,the number of crosslinks formed by crosslinking the styrenic blockcopolymer via the crosslinkable sites present in the hard polymer block(A) can be controlled by adjusting the number of functional groups,i.e., either the (i) alkylstyrene-derived structural units or the other(ii) functional groups, introduced into the hard polymer block (A)and/or the amount of crosslinking agent utilized. The number ofcrosslinks in the hard polymer block (A) of the styrenic block copolymeris preferably 2 or more per molecule of the styrenic block copolymer.

Other aromatic vinyl compound units can be present in the hard polymerblock (A) other than the alkylstyrene-derived structural unit. Theexamples of such other aromatic vinyl compounds include, but are notlimited to, units derived from styrene, α-methylstyrene,β-methylstyrene, t-butylstyrene, monofluorostyrene, difluorostyrene,monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene,vinylanthracene, indene, and acetonaphthylene. The styrenic blockcopolymer may have one or more of these units. Among them, styrene unitsare preferred as the other aromatic vinyl compound units.

When a hard polymer block (A) has aromatic vinyl compound units inaddition to the alkylstyrene-derived structural unit, the said units canbe combined in any form such as random form, block form, and taperedblock form.

Optionally, the hard polymer block (A) may further comprise smallamounts of structural units derived from other copolymerizable monomersin addition to the structural units derived from the aromatic vinylcompounds. The proportion of the structural units derived from othercopolymerizable monomers is generally 30% by weight or less, andpreferably 10% by weight or less based on the total weight of the hardpolymer block (A). Examples of other copolymerizable monomers include,but not limited to, methacrylic ester, acrylic ester, 1-butene, pentene,hexene, butadiene, isoprene, methyl vinyl ether, and other monomers.These other copolymerizable monomers may constitute any form such asrandom form, block form, and/or tapered block form.

As indicated hereinabove, the styrenic block copolymer also contains asoft polymer block (B) which comprises one or more or preferably two ormore, same or different, structural units. Soft polymer block (B) can bederived from monomer units such as derived from a conjugated dienecompound; or an olefin preferably having from 2 to about 12 carbonatoms, such as ethylene, propylene, butylene, etc., or a combinationthereof. When the soft polymer block (B) has structural units derivedfrom three or more repeat units, the structural units may be combined inany form such as random, tapered, block, or any combination thereof.

Non-limiting examples of conjugated diene compounds include isoprene,butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene.

In one embodiment, the soft polymer block (B) is an olefin blockcomprising monomer units from one or more, preferably two or more,different monomer units such as ethylene, propylene, butylene, or thelike. Preferred monomer combinations for soft polymer block (B) includeunits derived from ethylene and butylene monomers, and monomer unitsderived from ethylene and propylene monomers. The soft polymer block (B)units can be combined in any form such as random, tapered, block or anycombination thereof.

In one embodiment, the soft polymer block (B) is a polyisoprene blockcomprising monomer units mainly containing isoprene units, or acorresponding hydrogenated polyisoprene block in which part or all ofthe unsaturated bonds of the polyisoprene block are hydrogenated; apolybutadiene block comprising monomer units mainly containing butadieneunits, or a corresponding hydrogenated polybutadiene block in which partor all of the unsaturated bonds of the polybutadiene block arehydrogenated; or an isoprene/butadiene copolymer block comprisingmonomer units mainly containing isoprene units and butadiene units, or acorresponding hydrogenated isoprene/butadiene copolymer block in whichpart or all of the unsaturated bonds thereof are hydrogenated. Thepolymer block (B) is more preferably a hydrogenated block of thepolyisoprene block, the polybutadiene block, or the isoprene/butadienecopolymer block.

In the polyisoprene block which can be a block of the polymer block (B),the units derived from isoprene include, before hydrogenation, at leastone group including a 2-methyl-2-butene-1,4-diyl group[—CH₂—C(CH₃)═CH—CH₂; 1,4-bonded isoprene unit], an isopropenylethylenegroup [—CH(C(CH₃)═CH₂)—CH₂—; 3,4-bonded isoprene unit], and a1-methyl-1-vinylethylene group [—C(CH₃)(CH═CH₂)—CH₂—; 1,2-bondedisoprene unit]. The proportions of individual units are not specificallylimited.

In the polybutadiene block which can be a block of the polymer block(B), it is preferred that, before hydrogenation, the butadiene unitsinclude from 70 to 20% by mole, and particularly from 65 to 40% by moleof 2-butene-1,4-diyl groups (—CH₂—CH═CH—CH₂—; 1,4-bonded butadieneunit); and from 30 to 80% by mole, and particularly from 35 to 60% bymole of vinylethylene groups [—CH(CH═CH)—CH₂—; 1,2-bonded butadieneunit]. When the amount of the 1,4-bonds in the polybutadiene block iswithin the above-specified range of 70 to 20% by mole, the rubberproperties become further satisfactory.

In the isoprene/butadiene copolymer block which can be a block of thepolymer block (B), the units derived from isoprene include, beforehydrogenation, at least one of a 2-methyl-2-butene-1,4-diyl group, anisopropenylethylene group, and a 1-methyl-1-vinylethylene group, and theunits derived from butadiene include a 2-butene-1,4-diyl group and/or avinylethylene group. The proportions of individual units are notspecifically limited. The arrangement or configuration of the isopreneunits and the butadiene units in the isoprene/butadiene copolymer blockcan be any form such as random form, block form, and tapered block form.To further effectively improve the rubber properties, the molar ratio ofthe isoprene units to the butadiene units is preferably in a range from1:9 to 9:1, and more preferably in a range from 3:7 to 7:3.

In a preferred embodiment, part or all unsaturated double bonds in thesoft polymer block (B) of the styrenic block copolymer are hydrogenated.The hydrogenation ratio is generally 60% by mole or more desirably 80%by mole or more, and preferably 100% by mole. When the hydrogenationratio is approximately 100% by mole, the reactivity between the softpolymer block (B) and the crosslinking agent decreases and, thereforethe crosslinkability between the at least one alkylstyrene-derivedstructural unit and the functional group of hard polymer block (A) withthe crosslinking agent increases in dynamic vulcanization for thepreparation of a thermoplastic vulcanizate of the present invention.

Optionally, the soft polymer block (B) can further include small amountsof structural units derived from other copolymerizable monomers inaddition to the structural units described herein. In this case, theproportion of the other copolymerizable monomers is generally 30% byweight or less, and preferably 10% by weight or less based on the totalweight of the soft polymer block (B) of the styrenic block copolymer.The examples of other copolymerizable monomers include, for example,styrene, p-methylstyrene, α-methylstyrene, and other monomers that canundergo ionic polymerization.

The styrenic block copolymers of the present invention are distinguishedfrom conventional crosslinkable products of block copolymers whichcomprise an aromatic vinyl compound polymer block and a soft block whichare crosslinked in the soft polymer block as the styrenic blockcopolymers of the present invention are at least crosslinkable throughthe hard polymer block.

In one embodiment, before hydrogenation, if any, and dynamicvulcanization, the number-average molecular weight of hard polymer block(A) is generally from about 2,500 to about 75,000, and preferably fromabout 5,000 to about 50,000; the number-average molecular weight of thesoft polymer block (B) is generally from about 10,000 to about 300,00,and preferably from about 30,000 to about 250,000; and the totalnumber-average molecular weight of the entire styrenic block copolymeris generally from about 12,500 to about 2,000,000, and preferably fromabout 50,000 to about 1,000,000. The number average molecular weight isdetermined by gel permeation chromatography based on a standardpolystyrene calibration curve. Preferred at least hard blockcrosslinkable styrenic block copolymers are described in U.S. Pat. No.7,074,855, herein fully incorporated by reference. One styrenic blockcopolymer suitable for use in the present invention is commerciallyavailable as Septon V from Kuraray Co., Ltd. of Tokyo, Japan.

Non-Olefin Thermoplastic Polymers and Copolymers

The compositions of the present invention include at least onenon-olefin thermoplastic polymers or copolymers such as polyamidepolymer or copolymer, poly(ester) or a copolymer thereof, poly(phenyleneoxide) or a copolymer thereof, poly(phenylene sulfide) or a copolymerthereof, poly(imide) or a copolymer thereof, poly(sulfone) or acopolymer thereof, etc. The term polymer when utilized within thisapplication, including the claims, refers to either a polymer orcopolymer, unless specifically stated otherwise.

Polyamides or nylons are characterized by the presence of an amidegroup, i.e., (—C(O)NH—). Polyamides which can be used in the presentinvention of one embodiment include, but are not limited to, polymersand copolymers, for example, formed by polycondensation of a diaminehaving from 4 to about 12 carbon atoms, and a diabasic acid ordicarboxylic acid having from 4 to 12 carbon atoms, selfpolycondensation of an amino acid, or polymerization of a lactam, i.e.,ring-opening polymerization. Polyamides have also been obtained bypolymerizing a monoamino-monocarboxylic acid, or a lactam thereof,having at least 4 carbon atoms, or by polymerizing a monoaminocarboxylic acid or a lactam thereof having at least 4 carbon atomstogether with substantially equimolar proportions of a diamine and adicarboxylic acid.

Examples of aminocarboxylic acids and lactams include aminocaproic acid,butyrolactam, pivalolactam, caprolactam, capryllactam, enantholactam,undecanolactam, dodecanolactam and 3- or 4-aminobenzoic acids.

Diamines suitable for use in the preparation of the polyamides includethe straight chain and branched, alkyl, aryl and alkyl-aryl diamines.Such diamines include, for example, ethylenediamine, propylenediamine,tetramethylenediamine, pentamethylenediamine, hexamethylenediamine andthe like. Also included are diamines such as2-methylpentamethylenediamine, isomeric trimethylhexamethylenediamine,meta-xylylenediamine, para-xylylenediamine,1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane,1,3-diaminocyclohexane, 1,4-diamino-cyclohexane,bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane,1,4-piperazine, meta-phenylenediamine, paraphenylenediamine,bis(4-aminophenyl)methane, and the like.

The dicarboxylic acids maybe aromatic or aliphatic dicarboxylic acids ofthe formula: HOOC—Z—COOH, wherein Z represents a divalent aliphaticgroup containing at least 2 carbon atoms or an aromatic group containingat least 6 carbon atoms. Examples of such acids are sebacic acid,suberic acid, azeleic acid, glutaric acid, pimelic acid, adipic acid,terephthalic acid, isophthalic acid and the like.

The polyamides suitable for use in the present invention are eithercommercially available or can be produced by methods known in the art.Specific examples of polyamides include, but are not limited to, nylons,such as polypropiolactam (Nylon-3), polypyrrolidinone (Nylon-4),polycaprolactam (Nylon-6), polyenantholactam (Nylon-7), polycapryllactam(Nylon-8), polyaminoundecanoic acid (Nylon-11), polylauryllactam(Nylon-12), polytetramethyleneoxalamide (Nylon-4,2)polytetramethyleneadipamide (Nylon-4,6), polyhexamethyleneisophthalamide(Nylon-6,1), polyhexamethyleneadipamide (Nylon-6,6),polyhexamethyleneazelamide (Nylon-6,9), polyhexamethylenesebacamide(Nylon-6,10), polyhexamethylenedodecanoic acid (Nylon-6,12), caprolactamand hexamethyleneadipamide (Nylon-6/6,6), terpolyamide(Nylon-6/6,6/6,10), poly(hexa-methylenediamineterephthalamide),poly(hexamethylenediamine isophthalamide), xylene-group containingpolyamides, and combinations or copolymers thereof. The polyamides arecommercially available from sources such as DuPont, BASF, Honeywell,EMS, Firestone, Solutia, Ticona, Arkema, Rhodia, DSM, and Degussi undervarious designations. Preferred polyamides are Nylon-6, Nylon-11,Nylon-12, Nylon-6,6, Nylon-6,9, Nylon-6,10 and Nylon-6/6,6.

Polyesters are characterized by the presence of an ester group, i.e.,(—C═(O)—O—). Polyesters which can be used in the present invention offurther embodiment include, but are not limited to, polymers andcopolymers, such as Glyptal polyesters, unsaturated polyesters,poly(ethylene terephthalate), poly(butylene terephthalate),glycol-modified polyester (PETG), poly(carbonate), poly(ether ester)block copolymers, and combinations or copolymers thereof.

Poly(phenylene oxide)s or poly(ethers) are characterized by the presenceof an ether group, i.e., (R—O—R). Polyethers which can be used in thepresent invention of further embodiment include, but are not limited to,polymers and copolymers, such as poly(phenylene oxide),poly(oxymethylene), acetal copolymer of formaldehyde, epoxyresins(ethoxylene resins), Furan resins, and combinations or copolymersthereof.

Poly(phenylene sulfides) are characterized by the presence of an sulfidegroup. Polyphenylene sulfides which can be used in the present inventionof further embodiment include, but are not limited to, polymers andcopolymers, such as poly(phelylene sulfide) and combinations orcopolymers thereof.

Poly(imides) are characterized by the presence of an imide group.Polyimides which can be used in the present invention of furtherembodiment include, but are not limited to, polymers and copolymers,such as polyamide-imides, modified polyimides, polyether-imides,polyamide-imide, and combinations or copolymers thereof.

Poly(sulfones) are characterized by the presence of a sulfone group.Polysulfones which can be used in the present invention of furtherembodiment include, but are not limited to, polymers and copolymers,such as poly(aryl sulfone), poly(ether sulfone), poly(phenyl sulfone),and combinations or copolymers thereof.

The polymers and copolymers for use in the present invention can beproduced by methods known in the art and/or are commercially availablefrom sources such as DuPont, BASF, Honeywell, EMS, Firestone, Solutia,Ticona, Arkema, Rhodia, DSM, Degussa, General Electric, Asahi-Kaseiunder various trade names.

The one or more non-olefin thermoplastic polymers are present in a totalamount generally from about 10 to about 1,500 parts, desirably fromabout 15 or about 90 to about 1,000 or about 900 parts, and preferablyfrom about 100 to about 850 parts per 100 parts by weight of thestyrenic block copolymer having at least the reactive hard block in thecompositions of the present invention. In an embodiment wherein thecomposition is a thermoplastic elastomer composition, and thus free of acrosslinking agent, the non-olefin thermoplastic such as polyamidepolymer or copolymer is present in an amount desirably from about 100 toabout 800 parts, and preferably from about 150 to about 800 parts byweight based on 100 parts by weight of the styrenic block copolymer. Inan embodiment wherein the composition is a thermoplastic vulcanizate andincludes a crosslinking agent, wherein the composition is crosslinked orable to be crosslinked, the non-olefin thermoplastic polymer orcopolymer is present in an amount desirably from about 10 to about 600parts, and preferably from about 15 to about 500 parts by weight basedon 100 parts by weight of the styrenic block copolymer in thecomposition.

The styrenic block copolymer and/or the graft functionalized styrenicblock copolymer may be hydrogenated by any process known in the art.Hydrogenation can be selective.

In a preferred embodiment, the compositions of the present invention aresubstantially free of a polyolefin polymer or copolymer. That is,preferably less than 5 parts by weight, desirably less than 3 parts byweight, and preferably less than 1 part by weight of a polyolefin ispresent per 100 parts by weight of the styrenic block copolymer in thecomposition. Most preferably, the composition is free of polyolefin.

Compatibilizer

The compatibilizer or compatibilizing agent of the present invention canbe an oligomer, polymer or copolymer, and preferably is a graft or blockcopolymer. It is preferably derived from components including (a) afunctionalized styrenic block copolymer (b) a non-olefin thermoplasticpolymer, which is or can be functionalized to include at least onefunctional group per chain, and optionally (c) a linking compound whichis utilized when (a) and (b) functional groups are the same or arenon-reactive with each other. Thus, the linking compound is not utilizedwhen the styrenic block copolymer and the non-olefin thermoplasticpolymer contain complementary reactive functional groups capable ofreacting with each other. Optionally, the compatibilizer is a graft orblock copolymer derived from the reaction of a linking compound which isgrafted to the backbone of a styrenic block copolymer, and thenon-olefin thermoplastic polymer is grafted or otherwise connected tothe styrenic block copolymer. By using such a non-olefin thermoplasticpolymer grafted styrenic block copolymer as a compatibilizing agent, itis possible to improve the compatibility of a blend comprising astyrenic block copolymer and a non-olefin thermoplastic polymer.

A. Compatabilizer Segment for, i.e., Compatible with, the Styrenic BlockCopolymers having at Least One Reactive Hard Block

Suitable compatibilizer segments for the styrenic block copolymers,prior to functionalization by compounds, such as maleic anhydride, canbe a styrenic block copolymer having a varying structure containingvarious ratios of olefin to aromatic vinyl units or functionalizedaromatic vinyl units, which can be the same or different than thefunctional groups (i) and (ii) described hereinabove with respect to theat least crosslinkable hard block. Thus, multiblock copolymers may beutilized which are a diblock copolymer, a triblock copolymer or a higherblock copolymer having the one or more soft blocks and the one or morehard blocks arranged in substantially any order. A preferredcompatibilizer segment for the styrenic block copolymer is an acid oranhydride functionalized block copolymer that is prepared bygraft-reacting an acid moiety or its derivative onto the hydrogenatedblock copolymer via a free radically initiated reaction. Suitablemonomers which may be grafted include unsaturated mono- andpolycarboxylic acids and anhydrides containing from about 3 to about 10carbon atoms. Examples of such monomers are fumaric acid, itaconic acid,citraconic acid, acrylic acid, maleic anhydride, itaconic anhydride, andcitraconic anhydride, or the like. The preferred grafting monomer ismaleic anhydride. The grafted block copolymer generally contains from0.1 to 10 percent by weight, and preferably about 0.2 to 5 percent byweight of grafted monomer, based on the total weight of the polymer.

The grafting reaction can be carried out in solution or by melt-mixingthe base block copolymer and the acid/anhydride monomer in the presenceof a free radical initiator as known in the art, see for example U.S.Pat. No. 6,653,408, herein fully incorporated by reference. The aromaticvinyl repeat unit can vary in an amount that ranges from about 1 toabout 99% by weight and preferably from about 22 to about 40% by weight,based on the total weight of the block copolymer. Suitable blockcopolymers are available from KRATON Polymers, Kuraray, Asahi-Kasei,BASF and the like. A preferred component is a linear triblock copolymerbased on styrene and ethylene/butylene, having a polystyrene orfunctionalized polystyrene content of 20-40%, and a maleic anhydrideweight of 1.4 to 2% based on the total weight of the block copolymer.One such polymer is available from Kraton Polymers under the trade nameKraton® 1901X.

B. Compatibilizer Segment for, i.e. Compatible with, the Non-OlefinThermoplastic Polymers or Copolymers

Non-olefin thermoplastic polymers suited for use in forming thecompatibilizer of the present invention include the non-olefinthermoplastic polymers described hereinabove, namely polyamide, or acopolymer thereof, poly(ester) or a copolymer thereof, poly(phenyleneoxide) or a copolymer thereof, poly(phenylene sulfide) or a copolymerthereof, poly(imide) or a copolymer thereof, poly(sulfone) or acopolymer thereof, etc. Suitable compatibilizer non-olefin thermoplasticpolymers or copolymers with or without a functional group arecommercially available. For example, polyamides include an amine groupwhich can be reacted with a maleic anhydride group of a functionalizedstyrenic block copolymer. Likewise, polyester prepolymers containingfunctional groups are available in the art, such as isocyanateterminated polyester prepolymer under the trade name MONDUR® from Bayer.Functionalized nitrile rubbers, acrylic rubbers and acrylate rubbersavailable from Bayer, Nippon Zeon, DuPont and others can also be used asa compatibilizer segment for non-olefin thermoplastic polymers orcopolymers.

C. Linking Compounds

One or more linking or bridging compounds can be utilized to impartfunctional groups to the styrenic block copolymer or non-olefinthermoplastic polymer, or a combination thereof. Preferably, thefunctionalized styrenic block copolymer and functionalized non-olefinthermoplastic polymer react to form the compatibilizer of the presentinvention. In a further embodiment, if the functional groups of thefunctionalized styrenic block copolymer and functionalized thermoplasticpolymer are not reactive with each other, a linking compound having twoor more functional groups (same or different) reactive with bothpolymers is also utilized in the reaction to form the compatibilizer.

Each linking compound before reaction with the styrenic block copolymeror non-olefin thermoplastic has at least two reactive functional groupswhich can be the same or different. The examples include, but are notlimited to, an unsaturated hydrocarbon group, an amino group, anhydroxyl group, a carboxylic acid group, an anhydride group, an epoxygroup or an isocyanate group, or the like. For example, in oneembodiment wherein the non-olefin thermoplastic is a polyester, alinking compound having an epoxy group or an isocyanate group is reactedtherewith in order to produce a functionalized polyester polymer orcopolymer.

The linking compounds are generally monomers, but can be oligomers orpolymers or copolymers with one or more functional groups. Linkingcompounds can be the same or different than functional groups, which areused to functionalize the styrenic block copolymers and thethermoplastic polymer. Suitable linking compounds or functional groupsinclude, but not limited to, unsaturated carboxylic anhydrides,unsaturated amines, unsaturated carboxylic acids, epoxy group containingunsaturated compounds, and hydrolysable silyl group containingunsaturated compounds, diamines, isocyantes, polyols, and dicarboxylicacids.

Examples of unsaturated anhydrides include, but are not limited to,maleic anhydride, itaconic anhydride, citraconic anhydride, andbicyclo-2,2,1-hept-2-ene-5,6-dicarboxylic anhydride. Examples ofsuitable unsaturated carboxylic acids include, but are not limited to,acrylic acid, methacrylic acid, maleic acid, monomethyl maleate, fumaricacid, itaconic acid, citraconic acid, and crotonic acid. Examples ofepoxy group-containing unsaturated compounds include, but are notlimited to, glycidyl acrylate, glycidyl methacrylate and allyl glycidylether. Examples of hydrolyzable silyl group-containing unsaturatedcompounds include, but are not limited to, vinyl trimethoxysilane, vinyltriethoxysilane, vinyl triacetoxysilane,gamma-methacryloxypropyltrimethoxysilane or vinyltris(β-methoxyethoxy)silane. Examples of amines include, but are notlimited to, 3-amino cyclopentene, amino cyclohexanol, p-amino benzoicacid, ethylene diamine, propylene diamine, 1,4-butane diamine, and1,5-pentane diamine. The isocyanates of the present invention generallyhave the formula R(NCO)_(n), where n is an integer of about 2 to 4 andpreferably 2. R can be aromatic, cycloaliphatic, aliphatic, orcombinations thereof having from 2 to 20 carbon atoms. Examples ofisocyanates include, but are not limited to,diphenylmethane-4,4′-diisocyanate (MDI); toluene-2,4-diisocyanate(2,4-TDI); toluene-2,6-diisocyanate (2,6-TDI); methylene bis(4-cyclohexylisocyanate) (H₁₂MDI); m-xylene diisocyanate (XDI) and1,4-cyclohexyl diisocyanate (CHDI). Examples of dicarboxylic acidsinclude, but are not limited to, oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, and maleic acid. The polyols of thepresent invention are preferably diols having from 2 to about 20 carbonatoms and can be alkane diols, cycloaliphatic diols, alkylaryl diols,and the like. Examples of polyols include, but are not limited to,ethylene glycol, propylene glycol, 1,6 hexane diol, 1,3 butane diol, 1,5pentane diol, neopentyl glycol and 2-cyclopentane diol,hydroquinone-di(β-hydroxyethyl) ether (HOEE). The polyols can alsoinclude ether linkages which include compounds such as diethyleneglycol, dipropylene glycol, polytetramethylene ether, polypropyleneglycol, isocyanate-terminated polyethers or polyesters.

As indicated hereinabove, the compatibilizers of the present inventioncan be formed prior to addition to a blend of the present inventionincluding a styrenic block copolymer including at least onecrosslinkable hard block and a non-olefin thermoplastic, or can beformed in situ during the melt blending of the styrenic block copolymerhaving at least one crosslinkable hard block and a non-olefinthermoplastic polymer or copolymer, and/or dynamic vulcanizationthereof. When the compatibilizer is formed in situ, the compatibilizersegment for non-olefin thermoplastic can be the same as the blend orvulcanizate non-olefin thermoplastic. For example, the compatibilizercan be formed in situ from a polyamide, which contains a —NH₂ functionalgroup and a functionalized styrenic block copolymer including a maleicanhydride functional group.

The total amount of either the (a) one or more compatibilizers or (b)functionalized styrenic block copolymer that can be utilized incompositions of the present invention is in an amount from about 0 toabout 1000 parts by weight, desirably from about 0.5 to about 150 partsby weight and preferably from about 5 to about 50 parts by weight per100 parts by weight of the styrenic block copolymer having at least onereactive hard block. That is, the amounts above refer to acompatibilizer itself comprising the reaction product of (i) afunctionalized non-olefin thermoplastic or an elastomer, (ii) afunctionalized styrenic block copolymer or functionalized polymer orcopolymer compatible with the styrenic block copolymer having acrosslinkable hard block, and optionally, (iii) a linking compound, isadded to a composition of the present invention utilized to form a blendor a vulcanizate, or refers to the amount of functionalized styrenicblock copolymer that can be added to such compositions wherein thecompatibilizer is formed in-situ. In an embodiment where the compositionof the present invention is a thermoplastic elastomer blend and thusfree of a crosslinker, the (a) compatibilizer or (b) functionalizedstyrenic block copolymer is present desirably in an amount from about 5to about 300 parts, and preferably from about 10 to about 100 parts byweight based on 100 parts by weight of the styrenic block copolymer. Inan embodiment wherein the composition includes a crosslinking agent andthe composition is thus a thermoplastic vulcanizate after crosslinking,the (a) compatibilizer or (b) functionalized styrenic block copolymer ispresent in an amount desirably from about 0.5 to about 400 parts, andpreferably from about 1 to about 50 parts by weight per 100 parts byweight of the styrenic block copolymer.

Optional Components

The compositions of the present invention may further include otherpolymers or copolymers so long as the addition thereof does not decreasedesirable properties of the compositions of the present inventioncontaining the styrenic block copolymer containing at least one reactivehard block and non-olefin thermoplastic. Examples of other polymersinclude, but are not limited to, poly(methyl acrylate), poly(methylmethacrylate), and other acrylic resins; styrene homopolymers,acrylonitrile-styrene resins, acrylonitrile-butadiene-styrene resins,and other styrenic resins; polycarbonate resins. These copolymers mayalso include small amount of copolymers such as ethylene-propylenecopolymer rubbers (EPM), ethylene-propylene-non-conjugated dieneterpolymer rubbers (EPDM), and other ethylenic elastomers; otherstyrenic elastomers, hydrogenated products and modified productsthereof; hydrogenated products and modified products thereof; acrylicrubbers; isobutylene-isoprene rubbers (butyl rubbers);acrylonitrile-butadiene rubbers; silicone rubbers; fluorocarbon rubbers;urethane rubbers; polyurethane elastomers; polyamide elastomers; andpolyester elastomers. In a preferred embodiment, compositions of thepresent invention preferably contain less than or equal to 200 parts byweight of other polymers per 100 parts by weight of the styrenic blockcopolymer.

If desired, the compositions of the present invention may includelubricants, light stabilizers, pigments, heat stabilizers, anti foggingagents, anti-stat agents, silicone oils, antiblocking agents, UVabsorbers, anti-oxidents, flame retardants, processing aids, and fillerssuch as inorganic fillers. Examples of inorganic fillers for use in thecompositions of the present invention include, but are not limited to,one or more of calcium carbonate, talc, clay, silica, titanium oxide,carbon black, barium sulfate, mica, glass fibers, whiskers, carbonfibers, magnesium carbonate, magnesium hydroxide, glass powders, metalpowders, kaolin, graphite, molybdenum disulfide and zinc oxide. Theorganic fillers can be utilized within ranges not adversely effectingthe performance of the compositions and is generally about 50 parts byweight or less per 100 parts by weight of the styrenic block copolymer.

The compositions of the present invention can also optionally include arubber softener such as a mineral oil softener, or a synthetic resinsoftener, a plasticizer or combinations thereof. Oil softeners aregenerally mixes of aromatic hydrocarbons, naphthene hydrocarbons andparaffin hydrocarbons. Those in which carbon atoms constituting paraffinhydrocarbons occupy 50% by number or more of the total carbon atoms arecalled “paraffin oils”. Those in which carbon atoms constitutingnaphthene hydrocarbons occupy 30 to 45% by number of the total carbonatoms are called “naphthene oils”, and those in which carbon atomsconstituting aromatic hydrocarbons occupy 35% by number or more of thetotal carbon atoms are called “aromatic oils”. In one embodiment,paraffin oils and/or plasticizers are preferably utilized as a rubbersoftener in compositions of the present invention.

Examples of synthetic resin softeners include, but are not limited to,polybutenes and low molecular weight polybutadienes. The rubbersoftener, when present, ranges generally from about 0 to about 300 partsby weight, and preferably from about 10 to 100 parts by weight per 100parts by weight of the styrenic block copolymer.

As stated hereinabove, in one embodiment the composition of the presentinvention is a blend of the styrenic block copolymer and polyamide andpreferably, styrenic block copolymer derived compatibilizer, as well asany desired optional components prepared by heating the components ofthe composition to obtain a melted composition without degrading thecomponents thereof and mixing the composition. In a further embodiment,the compositions of the present invention are thermoplastic vulcanizatesthat are vulcanized, preferably dynamically vulcanized, under meltingconditions during which the composition is mixed and crosslinked due tothe inclusion of a crosslinking agent. Melt blending or vulcanization,or a combination thereof, is generally performed at a temperaturegenerally from about 160° C. to about 290° C., preferably from about200° C. to about 250° C. Melt extrusion times generally range from about20 to about 600 seconds, and preferably from about 30 to about 200seconds, and generally depends on the particular processing equipmentutilized and components of the composition.

The crosslinking agent of the present invention can be a crosslinkingagent that acts upon the (C₁-C₈ alkyl)styrene-derived functional unit inthe hard polymer block (A) and/or soft segments (B) to thereby formcrosslinks or a crosslinking agent that has a reactive group capable ofreacting with the functional group to form crosslinks. The crosslinkingagent is not specifically limited and can be any crosslinking agent solong as it can act upon the crosslinkable units in the hard segment (A)as well as soft segment (B) of the styrenic block copolymer duringvulcanization under melting conditions and thereby form crosslinks insitu in the hard polymer block (A) and/or soft segment (B). One can usetwo or more crosslinking agents to achieve desired performance.

If polymer block (B) is fully saturated, then only hard polymer (A) iscrosslinked in the presence of, for example, a bismaleimide compound.When at least one unsaturated double bond is present in the soft polymerblock (B), then both hard polymer block (A) and soft polymer block (B)can be crosslinked in the presence of a bismaleimide compound. Both hardpolymer block (A) and soft polymer block (B) are crosslinked by peroxideregardless of whether or not an unsaturated bond is present in the softpolymer block (B). The crosslinking agent can be appropriately selectedin view of reactivity depending on processing conditions such asprocessing temperature and processing time during dynamic vulcanization.Examples of suitable crosslinking agents include bismaleimide compoundsand organic peroxides.

Examples of suitable bismaleimide compounds include, but are not limitedto, N,N′-m-phenylene bismaleimide, N,N′-p-phenylene bismaleimide,N,N′-p-phenylene(1-methyl)bismaleimide, N,N′-2,7-naphthene bismaleimide,N,N′-m-naphthene bismaleimide, N,N′-m-phenylene-4-methyl bismaleimide,N,N′-m-phenylene(4-ethyl)bismaleimide, and tolylene bismaleimide.N,N′-m-phenylene bismaleimide is preferred from the viewpoint ofreactivity.

Examples of suitable organic peroxides include, but are not limited to,dicumyl peroxide, di-t-butyl peroxide,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,1,3-bis(t-butylperoxyisopropyl)benzene,3,3,5,7,7-pentamethyl, 2,4-trioxepane, and t-butyl cumyl peroxide.3,3,5,7,7-pentamethyl-1,2,4-trioxepane compound is preferred from theviewpoint of higher decomposition temperature.

Crosslinking activators or coagents can be optionally utilized ifdesired by the processor. Such coagents include, for example, triallylisocyanurate, divinylbenzene, ethylene glycol dimethacrylate,triethylene glycol dimethacrylate, and other polyfunctional monomers oroligomers or polymers.

In an embodiment where the functional group of the styrenic blockcopolymer includes an active hydrogen atom, such as a hydroxyl group,—SH, —NH₂, —NHR, —CONH₂, —CONHR, —CONH—, —SO₃H, —SO₂H, and —SOH, anisocyanate group containing a crosslinking agent can be utilized, suchas monomeric isocyanate, isocyanate adducts such as aliphatic,alicyclic, aromatic, and biphenyl isocyanate adducts, and blockisocyanates. Preferred are polyisocyanate compounds having two or more,preferably three or more, isocyanate groups. A tin catalyst, a titaniumcatalyst, or another catalyst can be used for improving the reactivitybetween isocyanate crosslinking agents and a functional group of hardpolymer block (A) of the styrenic block copolymer.

When the functional group in the hard polymer block (A) is a hydroxylgroup, a crosslinking agent can be, for example, a polyepoxy compound,acid anhydride such as maleic anhydride, a polycarboxylic anhydride oran isocyanate compound. When the functional group in the hard polymerblock (A) is a carboxyl group, the crosslinking agents can include, forexample, polyepoxy compounds and polyamines. When the functional groupin the hard polymer block (A) is an epoxy group, suitable crosslinkingagents include polycarboxylic acids and polyamines.

The amount of crosslinking agent or one or more crosslinking agents inthe composition ranges generally from about 0.01 to about 20 parts,desirably from about 0.1 to about 10 parts, and preferably from about0.1 to about 5 parts per 100 parts by weight of the styrenic blockcopolymer. Alternatively speaking, in terms of equivalents of thefunctional group of the styrenic block copolymer, the amount of thecrosslinking agent is preferably from about 0.1 to 100 equivalents, andpreferably from 0.1 to 10 equivalents per equivalent of the functionalgroup in the hard polymer block (A) or per total equivalent of thefunctional groups in the hard polymer block (A) and, if any, in the softpolymer block (B).

Composition Preparation

As indicated herein, the dynamic vulcanization process preferablyutilized in one embodiment is to induce vulcanization of the styrenicblock (A) and soft rubber block (B). Other vulcanization methods can beutilized. Dynamic vulcanization is preferably performed by mixing thecomponents of the composition to disperse the components preferablyhomogeneously, above the melting point of the composition. Then one ormore components of the mixtures are vulcanized under dynamic mixingconditions.

Compositions of the present invention can be prepared in a Banbury, tworoll mill, or a continuous mixer such as single screw or twin screwmixer, Buss Kneader or any other suitable mixing machines. After thepreparation of the compound, they can be pelletized or diced usingappropriate equipment.

In one embodiment, thermoplastic elastomers are prepared by meltblending appropriate components such as styrenic block copolymer,non-olefin thermoplastics, compatibilizer or compatibilizer formingcomponents, stabilizer, etc, in a twin screw mixer above the meltingpoint of the plastics. In another embodiment, styrenic block copolymerand thermoplastic such as polyamide, compatibilizer or compatibilizerforming components and other additives are added through the feedhoppers to a twin screw mixer and crosslinking agents are introducedafter the thermoplastic is melted under dynamic mixing conditions tocomplete the vulcanization process. If one uses a batch process,styrenic block copolymer, and non-olefin thermoplastic such as polyamideand optionally other additives are melted and mixed thoroughly, thencrosslinking agents are introduced to crosslink at least the styrenicblock copolymer. The substantially homogeneous reaction mixture is thendischarged from the Banbury to cool down. The dynamic vulcanization canbe performed at a temperature within the ranges in which the styrenicblock copolymer and the polyamide are melted and the crosslinking agentreacts. Temperature ranges generally from about 160° C. to about 290°C., desirably from about 190° C. to about 270° C., and preferably fromabout 210° C. to about 250° C. Mixing time is preferably from about 20to about 600 seconds, desirably from about 20 to about 300 seconds, andpreferably from about 30 to about 200 seconds. The particles of adispersed phase when present have a diameter of generally from about 0.1to about 100 μm, desirably from about 0.1 to about 50 μm, and preferablyfrom about 0.1 to about 10 μm. The dynamically vulcanized composition isa thermoplastic and is able to be molded and remolded utilizing any ofvarious processes.

In the case where the composition of the present invention does notinclude a crosslinking agent, the composition is a blend of the styrenicblock copolymer, a thermoplastic such as polyamide and any othercomponents present, preferably in a fine or substantially homogeneousmix.

The blended compositions of the present invention can be molded orprocessed utilizing a molding procedure such as injection molding,compression molding, extrusion molding blow molding, rotational molding,calendering, and the like.

Additional Vulcanizates Including Polyolefin and Non-PolyolefinComponents

In yet a further embodiment of the present invention, a thermoplasticvulcanizate composition is provided comprising the styrenic blockcopolymer having at least one reactive or crosslinkable hard block (A)as described hereinabove, a polyolefin polymer or copolymer, anon-olefin thermoplastic polymer or copolymer, and a compatibilizingagent. Various thermoplastic vulcanizates comprising styrenic blockcopolymers and polyolefins are known in the art. Such compositions, dueto the polyolefin, have a relatively low upper use temperature range. Byincluding a non-olefin thermoplastic polymer or copolymer, such as apolyamide, a composition having a high melting point and thus anincreased upper use temperature service range is provided. Acrosslinking agent is also provided in the composition in order toproduce dynamic vulcanization.

Polyolefins suitable for use in the thermoplastic vulcanizatecompositions of this embodiment include, but are not limited to,ethylene polymers, propylene polymers, polybutene-1,poly-4-methylpentene-1, or the like. The polyolefins can be used aloneor in combination. Ethylene polymers for example include high-densitypolyethylenes, medium-density polyethylenes, low-density polyethylenes,and other ethylene homopolymers; ethylene-butene-1 copolymers,ethylene-hexene copolymers, ethylene-heptene copolymers, ethylene-octenecopolymers, ethylene-4-methylpentene-1 copolymers, ethylene-vinylacetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylatecopolymers, ethylene-methacrylic acid copolymers, ethylene-methacrylatecopolymers, and other ethylene copolymers. Polypropylene polymersinclude for example propylene homopolymers; ethylene-propylene randomcopolymers, ethylene-propylene block copolymers, propylene-butene-1copolymers, propylene-ethylene-butene-1 copolymers, andpropylene-4-methylpentene-1 copolymers.

Styrenic block copolymer thermoplastic vulcanizate compositions includethe polyolefin in an amount generally from about 0.5 to about 200,desirably from about 20 to about 100, and preferably from about 30 toabout 80 parts by weight based on 100 parts of the total weight of thestyrenic block copolymer having the at least a crosslinkable hard block.The remaining required components of the composition, namely, thenon-olefin thermoplastic polymer and the compatibilizer are present inthe amounts set forth hereinabove with respect to the non-olefincontaining embodiments.

As with the above embodiments, the compatibilizer added to thecomposition can be formed prior to addition thereto, or in situ asdescribed, such as by reaction of a functionalized styrenic blockcopolymer such as maleic anhydride functionalized styrenic blockcopolymer and a non-olefin thermoplastic, such as a polyamide, reactedtherewith. Dynamic vulcanization can be performed as describedhereinabove. In one embodiment, the styrenic block copolymer having atleast a crosslinkable hard block (A) can be dynamically vulcanized inthe presence of the polyolefin and later melt blended with the othercomponents of the composition. Obviously, variations of the process canfurther be utilized.

Molded articles obtained by molding the compositions of the presentinvention can be used in various applications such as automotive, softtouch overmoldings, extrusions and co-extrusions, building andconstruction, appliances, electrical, industrial, medical, food andpotable water contact goods, housewares, sporting goods, consumer, andindustrial applications, but not limited thereto. For example, themolded articles can be used in instrumental panels, center panels,center console boxes, door trims, pillars, assist grips, steeringwheels, airbag covers, air ducts, soft touch overmoldings, and otherinterior automotive trims; weather strips, bumpers, moldings, sealingmaterials between glass and frames, and other exterior automotive trims;remote control switches, office equipment, stereos, home-applianceparts; hydroscopes, underwater camera covers, and other underwaterproducts; covering parts, industrial parts, for example, for sealing,waterproofing, soundproofing, and vibration isolation; racks, pinionboots, suspension boots, constant velocity joint boots; and otherautomotive functional parts; belts, hoses, tubes; wire covering,silencer gears, and other electric/electronic parts; sporting goods;sundry goods; stationery; doors, window frame materials, and otherconstruction materials; joints; valve parts; gaskets for medicalsyringes, bags, tubes, and other medical appliances; hot melt sealingmaterials; rubber threads, stretchable films, and other stretchablematerials; wires, cables, and other articles.

EXAMPLES

The present invention is illustrated in further detail with respect tothe examples set forth herein, which are not intended to limit the scopeof the invention.

The following example compositions were prepared from components as setforth in Table I below. The components of each respective compositionwere melt mixed at about 230° C. in a Banbury batch mixer in theproportion shown in Table I to yield a thermoplastic elastomercomposition. No crosslinking agent was present.

Test specimens for the tests conducted below were formed by compressionmolding at about 232° C. The physical properties were determinedaccording to the test method below and the results are also shown inTable I. The results show that thermoplastic elastomer blendcompositions can be prepared including a blend of polyamide and styrenicblock copolymer, with and without a compatibilizer (formed in situ bythe reaction between acid modified styrenic block copolymer andpolyamide). Example 1 is the composition without compatibilizer. Example2 is the composition with compatibilizer of the present invention.Compared to the Example 1 composition, Example 2 shows higher tensileproperty and has better tensile retention after 22 hours at 150° C. inIRM 903 Oil. Both compositions survived in oil at 150° C.

TABLE I Raw Material Example 1 Example 2 Polyamide¹ 52.7 52.7 StyrenicBlock Copolymer² 47.3 47.3 Functionalized Styrenic Block Copolymer³ —10.00 Stabilizer⁴ 1.00 1.00 Stabilizer⁵ 1.00 1.00 Lubricant⁶ 1.00 1.00Total Weight % 103.00 113.00 Tests Performed Tensile Strength (psi)(ASTM D-412) 1810 6010 Elongation Break (%) (ASTM D-412) 11 400 TensileStrength (psi) (After 22 hrs at 150° C. in 610 3150 IRM 903 Oil) (ASTMD-412) Elongation Break (%) (After 22 hrs at 150° C. in 1 130 IRM 903Oil) (ASTM D-412) Hardness D (instantaneous)(ASTM D-2240) 60 66 HardnessD (5 sec. delay) (ASTM D-2240) 56 63 ¹Nylon 6 from Honeywell of NewJersey ²SEPTON V from Kuraray Co. Ltd. of Tokyo, Japan ³AcidFunctionalized Styrenic Block Copolymer from Kraton Polymers of Houston,TX ⁴Irganox 1010 from Ciba Specialty Chemical ⁵Ethanox from 330Albemarle Corp. ⁶Stearic Acid from Honeywell Inernational.

Table II sets forth thermoplastic vulcanizate compositions prepared fromthe components as set forth therein. The TPVs used as one component inexamples 3 to 5 were prepared from in situ dynamic vulcanization bycrosslinking the styrenic block copolymer in the presence ofpolypropylene above melting point of polypropylene. The mixture ofcomponents used to form the TPV included the styrenic block copolymer(100 phr, Septon V from Kuraray Co.), polypropylene (35 phr, Profax fromBasell), antioxidants (0.4 phr, Irganox 1010 from Ciba Specialty) andperoxide (1.7 phr, Vulcup 40KE from Geo). The mixture was then fed to atwin screw mixer to achieve homogeneous molten mixture above the meltingpoint of polypropylene and in situ dynamic vulcanization took place bycrosslinking the hard block (A) and the soft block (B) of the styrenicblock copolymer as a crosslinking agent was present in the homogeneousmolten mixture. The resulting TPV composition was then pelletized toform pellets which were then used in the following examples of thepresent invention.

The components of each example were premixed in the proportions shown inTable II and each resulting composition was individually fed to a twinscrew extruder where the composition was melted and mixed at atemperature of about 240° C. for about 200 seconds to achievehomogeneous mixture. The physical properties of the thermoplasticvulcanizate compositions were determined according to the test methodsbelow. Results are also shown in Table II. The results show thatthermoplastic vulcanizate compositions can be prepared by melt mixingthe Uniprene TPV, polyamide and acid functionalized styrenic blockcopolymer. Compatibilizer of the current invention was formed in situunder melt mixing conditions above the melting point of polyamide as aresult of the reaction between polyamide and acid-functionalizedstyrenic block copolymer.

The properties are reported below. Example 3 is a comparative exampledynamically vulcanized by crosslinking the styrenic block copolymer inthe presence of polypropylene above the melting point of polypropyleneunder melt mixing conditions. Examples 4 and 5 are the compositions withcompatibilizer of the present invention. Compared to Example 3composition, examples 4 and 5 show higher tensile properties and hasbetter tensile retention after 22 hours at 150° C. in IRM 903 Oil. Testspecimens of control 3 disintegrated, but none of the test specimens ofthe current invention, examples 4 and 5, were disintegrated as a resultof improved oil resistance at 150° C.

TABLE II Control Raw Material Example. 3 Example 4 Example 5 TPVIncluding Crosslinked Styrenic Block Copolymer¹ 100.00 75.00 65.00Polyamide² — 20.00 30.00 Functionalized Styrenic Block Copolymer³ — 5.005.00 Total Weight % 100.00 100.00 100.00 Tests Performed TensileStrength (psi) (ASTM D-412) 2173 2334 2856 Elongation Break (%) (ASTMD-412) 412 306 302 Tensile Strength (psi) (After 22 hrs at 150° C. inDisintigrated 966 3300 IRM 903 Oil) (ASTM D-412) Hardness A or D (inst)(ASTM D-2240) A93 D51 D60 Hardness A or D (5 sec. delay) (ASTM D-2240)A91 D46 D55 Specific Gravity (ASTM D-792) 1.01 1.02 1.03 Modulus at 100%Elongation (ASTM D-412) — 1238 3604 ¹TPV derived from Septon V andpolypropylene ²Nylon 6 from Honeywell of New Jersey ³Acid FunctionalizedStyrenic Block Copolymer from Kraton Polymers of Houston, TX

Another set of examples of TPV compositions was prepared from componentsas set forth in Table III below. The components of each respectivecomposition were melt mixed in a Banbury batch mixer in the proportionshown in Table III to yield a thermoplastic vulcanizate composition ascrosslinking agent was present. The procedure was as follows. Styrenicblock copolymer, functionalized styrenic block copolymer as indicatedand polyamide were melt mixed for 3 minutes above the melting point ofpolyamide at about 230° C. The vulcanizing agent was then added andmixing was continued for 3 additional minutes. Stabilizers were thenadded and the composition was mixed then for additional 2 minutes, thenremoved from the Banbury and passed through a roll mill to form a sheet.This was then used for compression molding for evaluation. Theproperties are reported below. Example 6 is the composition withoutcompatibilizer. Example 7 is the composition with compatibilizer (formedin situ) of the present invention. Example 7 shows higher tensileproperty and has better tensile retention after 22 hours at 150° C. inIRM 903 Oil. The number of test bars was counted after 22 hours at 150°C. in IRM 903 Oil. Two of five test specimens of Example 6 weredisintegrated, but none of 5 test specimens of the current invention,Example 7, were disintegrated as a result of improved oil resistance at150° C.

TABLE III Raw Material Example 6 Example 7 Polyamide¹ 40.0   40.0 Functionalized Styrenic Block Copolymer²    8.0  Styrenic BlockCopolymer³ 60.0   52.0  Crosslinking agent⁴ 0.5    0.5  Stabilizer⁵ 0.5   0.5  Stabilizer⁶ 0.5    0.5  Lubricant⁷ 0.5    0.5  TOTAL [phr] 102.0  102.0  Tests Performed Specific Gravity [dimensionless] (ASTM D-412)0.96    0.98 Hardness Shore A [Instant/5 sec delay] (ASTM 91/90 89/89D-2240) Hardness Shore D [Instant/5 sec delay] (ASTM 24/23 23/23 D-2240)Tensile Strength @ 2.0 in/min [psi] 783 2,050   Plaques) (ASTM D-412)Tensile Elongation [%] (ASTM D-412) 30% 110% Tensile Strength @ 150°C./22 hrs in ASTM 903 290   990   oil @ 2.0 in/min [psi] Plaques) (ASTMD-412) Tensile Elongation [%] (ASTM D_412) 4   25   No. of Tensile bardisintegrated @ 150° C./22 hrs in 2    0   ASTM 903 oil [Out of total 5]¹Nylon 6 from Honeywell of New Jersey ²Maleic Anhydride FunctionalizedStyrenic Block Copolymer from Kraton Polymers of Houston, TX ³SEPTON Vfrom Kuraray Co. Ltd. of Tokyo, Japan ⁴3,3,5,7,7-Pentamethyl-1,2,4trioxepane from Akzo-Nobel of Texas ⁵Irganox 1010 from Ciba SpecialtyChemical ⁶Ethanox from 330 Albemarle Corp. ⁵Stearic Acid from HoneywellInernational.

In accordance with the patent statutes, the best mode and preferredembodiment have been set forth; the scope of the invention is notlimited thereto, but rather by the scope of the attached claims.

1. A thermoplastic composition, comprising: a styrenic block copolymercomprising at least one hard polymer block (A) and at least one softpolymer block (B), wherein at least one block of the at least one hardpolymer block (A) is crosslinkable and independently includes at leastone of (i) an alkyl styrene-derived functional unit and (ii) an aromaticvinyl compound unit having a functional group, wherein the soft polymerblock (B) includes at least one repeat unit derived from an olefin or adiene; a non-olefin thermoplastic polymer or copolymer in an amount fromabout 10 to about 1,500 parts per 100 parts by weight of the styrenicblock copolymer, and wherein the composition has less than 5 parts byweight of a polyolefin per 100 parts by weight of the styrenic blockcopolymer, wherein the non-olefin thermoplastic includes one or more ofpolyimide, polyester, poly(phenylene oxide), poly(phenylene sulfide),poly(imide) and poly(sulfone); and a compatibilizer derived from areaction of at least a) a compatibilizer styrenic block copolymer, thecompatibilizer styrenic block copolymer being different than thestyrenic block copolymer, the compatibilizer styrenic block copolymerhaving one or more aromatic vinyl derived hard blocks, one or more softblocks including at least one repeat unit derived from an olefin or adiene, and including one or more functional groups independently derivedfrom a compound including a carboxylic acid group or an anhydride group,wherein the compatibilizer functional groups are different than the (i)alkylstyrene-derived functional unit and (ii) the aromatic vinylcompound unit having a functional group; and b) the non-olefinthermoplastic polymer or copolymer, and wherein the composition is freeof a crosslinking agent.
 2. The composition according to claim 1,wherein the compatibilizer is present in an amount from about 0.5 toabout 1000 parts by weight per 100 parts by weight of the styrenic blockcopolymer.
 3. The composition according to claim 1, wherein thefunctional group of the (ii) aromatic vinyl compound unit is —OH, —SH,NH₂, NHR, —CONH₂, —CONN, —SO₃H, —SO₂H, —SOH, a functional group having anitrogen atom, a functional group having a carbonyl group, a functionalgroup having a thiocarbonyl group, an epoxy group, or a thioepoxy group,or a combination thereof, and wherein the (i) alkylstyrene-derivedfunctional unit has at least one alkyl group containing from 1 to about8 carbon atoms, wherein the non-olefin thermoplastic is present in anamount from about 10 to about 600 parts per 100 parts by weight of thestyrenic block copolymer, and wherein the functionalized styrenic blockcopolymer segment of the compatibilizer is present in an amount fromabout 0.5 to about 1000 parts per 100 parts by weight of the styrenicblock copolymer.
 4. The composition according to claim 3, wherein thestyrenic block copolymer has the (i) alkylstyrene-derived functionalunit present in an amount of 1% by weight or more based on the totalweight of the hard polymer block (A), or has the functional group of the(ii) aromatic compound unit in an amount of 1.5 groups or more permolecule of the styrenic block copolymer, or a combination thereof. 5.The composition according to claim 4, wherein the alkylstyrene-derivedfunctional unit is p-methyl styrene, wherein the functional group of the(ii) aromatic vinyl compound unit is a hydroxyl group, wherein at leastone soft polymer block repeat unit is derived from ethylene, propylene,butylene or butadiene, and wherein at least one soft polymer block iscrosslinkable.
 6. The composition according to claim 1, wherein thecomposition is a thermoplastic elastomer, wherein the non-olefinthermoplastic is present in an amount from about 100 to about 800 partsper 100 parts by weight of the styrenic block copolymer.
 7. Thecomposition according to claim 4, wherein the composition is athermoplastic elastomer, wherein the non-olefin thermoplastic is orcopolymer is polyamide and is present in an amount from about 100 toabout 800 parts per 100 parts by weight of the styrenic block copolymer,and wherein the composition has less than 3 parts by weight ofpolyolefin per 100 parts by weight of the styrenic block copolymer. 8.The composition according to claim 1, wherein the composition is athermoplastic elastomer, wherein the non-olefin thermoplastic is presentin an amount from about 100 to about 800 parts per 100 parts by weightof the styrenic block copolymer, wherein the compatibilizer styrenicblock copolymer is present in an amount from about 0.5 to about 400parts per 100 parts by weight of the styrenic block copolymer, andwherein the composition has less than 1 part by weight of a polyolefinper 100 parts by weight of the styrenic block copolymer.
 9. A processfor producing the thermoplastic composition according to claim 1,wherein the process comprises the step of mixing components of thecomposition above the melting point of the non-olefin thermoplasticpolymer or copolymer.
 10. A process for producing the thermoplasticcomposition according to claim 4, wherein the process comprises the stepof mixing components of the composition above the melting point of thenon-olefin thermoplastic polymer or copolymer.
 11. A molded articlecomprising the composition of claim
 1. 12. A molded article comprisingthe composition of claim
 4. 13. The composition according to claim 1,wherein the compatibilizer is formed in situ from the compatibilizerstyrenic block copolymer and a polyamide which is present as thenon-olefin thermoplastic polymer or copolymer.
 14. The compositionaccording to claim 13, wherein the compatibilizer is present in anamount from about 0.5 to about 1000 parts by weight per 100 parts byweight of the styrenic block copolymer.
 15. The composition according toclaim 13, wherein the composition is a thermoplastic elastomer, whereinthe non-olefin thermoplastic is present in an amount from about 5 toabout 800 parts per 100 parts by weight of the styrenic block copolymer,and wherein the compatibilizer is present in an amount from about 0.5 toabout 1000 parts per 100 parts by weight of the styrenic blockcopolymer.
 16. A molded extruded, thermoformed or calendered articlecomprising the composition of claim 13.